WO2013129771A1 - Gazéifieur de biomasse à lit fixe doté d'un orifice d'injection de gaz tourbillonnant - Google Patents

Gazéifieur de biomasse à lit fixe doté d'un orifice d'injection de gaz tourbillonnant Download PDF

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Publication number
WO2013129771A1
WO2013129771A1 PCT/KR2013/000305 KR2013000305W WO2013129771A1 WO 2013129771 A1 WO2013129771 A1 WO 2013129771A1 KR 2013000305 W KR2013000305 W KR 2013000305W WO 2013129771 A1 WO2013129771 A1 WO 2013129771A1
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WO
WIPO (PCT)
Prior art keywords
gasification
chamber
fuel
gasifier
gas
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PCT/KR2013/000305
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English (en)
Korean (ko)
Inventor
이시훈
Original Assignee
전북대학교산학협력단
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Publication of WO2013129771A1 publication Critical patent/WO2013129771A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C10J3/30—Fuel charging devices
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/06—Catalysts as integral part of gasifiers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/15—Details of feeding means
    • C10J2200/152—Nozzles or lances for introducing gas, liquids or suspensions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/15—Details of feeding means
    • C10J2200/156—Sluices, e.g. mechanical sluices for preventing escape of gas through the feed inlet
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • C10J3/34—Grates; Mechanical ash-removing devices
    • C10J3/40—Movable grates
    • C10J3/42—Rotary grates

Definitions

  • the present invention relates to a fixed bed biomass gasification apparatus having a swirl gas inlet formed therein, and more particularly, to form a swinging gas inlet at a lower side of a gasification reactor in which a gasification reaction is performed by receiving wood-based biomass. It is possible to increase the contact time between the turning gasification agent and the pyrolysis layer to promote gasification, and by installing a catalyst chamber in the portion where the syngas outlet is formed, the tar component contained in the syngas discharged is further added.
  • the present invention relates to a biomass gasifier for converting into syngas.
  • the biomass is a term that refers to a bioorganism including plants, cells, and animals that eat and live by photosynthesis of plants and microorganisms that receive solar energy. Therefore, it has a comprehensive meaning from starch-based resources such as biomass grains, cellulose-based resources including forest products and farmer products such as rice straw and chaff, sugar-based resources such as sugar cane and sugar beet and food waste. .
  • biomass is an attractive energy source compared to fossil fuels because of its essentially zero environmental impact from CO2.
  • Biomass as described above is considered as a key resource to replace petroleum through the use of fuel oil production through pyrolysis and synthesis gas production including hydrogen, and through the combination of various subsequent processes. It is difficult to expand the utilization because it is difficult to secure economic feasibility due to the large initial investment cost.
  • the biomass energy conversion process currently being developed includes a gasification process using a fixed bed, a fluidized bed, and a circulating fluidized bed, and a conventional biomass gasification process includes a gasifier, a reformer, a tar recovery tank, a wood liquor recovery tank, and a scrubber (registration).
  • a gasifier a reformer
  • a tar recovery tank a wood liquor recovery tank
  • a scrubber a scrubber
  • Patent 10-0742159 fluidized bed biomass pyrolysis and gasifiers that are operated at relatively low temperatures (500-900 ° C.) may be composed of fluidized bed gasifiers, cyclones, heat exchangers, etc.
  • Patent No. 10-0659497 there was an attempt to improve the purity by installing an additional tar removal system in the biomass gasification process.
  • the biomass gasifiers that have been developed and used in the past have improved utilization efficiency when the biomass resources of uniform size are used and additionally install low tar catalyst process, which increases the plant area and the temperature due to the direct injection of the gasifier.
  • There are disadvantages such as non-uniformity, and there is a problem that clogging may occur in the gasifier when supplying the waste wood discharged from the lumber as fuel.
  • the secondary gasifying agent is additionally supplied from the side to prevent the channeling phenomenon, the supply of the gasifying agent is made uniform, and the tar contained in the generated syngas. It is an object to provide an apparatus for converting components into syngas while increasing the amount of combustible gas produced while passing through the catalyst chamber.
  • a fuel supply device for continuously supplying wood-based biomass as a fuel, a fixed-bed gasification reactor for supplying the fuel to gasify the synthesis gas, and a cyclone for separating solid components in the synthesis gas discharged from the gasification reactor
  • the gasification reactor comprises: a fuel inlet formed at an upper end thereof; A gasification chamber in which gas supplied from the fuel inlet is combusted and pyrolyzed to form gas, and a syngas discharge port configured to discharge gasified syngas is formed at an upper side thereof; An introduction chamber positioned below the gasification chamber to collect ash discharged after the combustion or pyrolysis is completed from the gasification chamber, and a ash discharge outlet for discharging the collected ash on the side, and a gasification agent inlet for introducing a gasifier from the outside; ; A rotary stocker interposed between the gasification chamber and the introduction chamber to partition the two spaces, and having a plurality of through holes formed in multiple stages by a rotating shaft to rotate and supply
  • the fixed bed biomass gasification apparatus is provided with a swirl gas inlet of the present invention by the above solution means,
  • the gasification agent was supplied in two directions, vertical and swiveling, to ensure uniform supply while preventing channeling as much as possible, so that even gasification was performed in the gasification layer in the gasification reactor.
  • FIG. 1 is a block diagram of a fixed bed biomass gasifier according to an embodiment of the present invention.
  • FIG. 2 is a schematic view showing a gasification reactor according to an embodiment of the present invention.
  • Figure 3 is a horizontal cross-sectional view of a gasification reactor showing a swirl gas inlet in accordance with an embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing a catalyst chamber according to an embodiment of the present invention.
  • Figure 5 is a graph showing the synthesis gas composition change produced by the operating time of the gasifier according to the present invention.
  • FIG. 1 is a block diagram of a fixed bed biomass gasifier according to an embodiment of the present invention
  • Figure 2 is a schematic diagram showing a gasification reactor according to an embodiment of the present invention.
  • the gasifier 1 of the present invention includes a fuel supply device 2 and a gasification reactor 3 in which gas is supplied from the fuel supply device.
  • the fuel supply device 2 supplies quantitatively woody biomass using a conveyor, screw, etc., and the woody biomass to be supplied is provided in various forms such as pellet form or powder or wood shredded. At this time, it is preferable that the fuel is supplied in a fixed amount so that the fixed bed height of the gasifier is maintained.
  • the gasification reactor 3 is a cylinder in which gasification is performed by a fixed bed method, and a fuel inlet 10 is formed at an upper end thereof.
  • the fuel inlet is provided with a valve 11 in the upper and lower double to form a temporary hopper space between the two valves to block the outside air from flowing directly into the gasification reactor when the fuel supply by the fuel supply device.
  • the valve 11 is supplied with fuel by opening the upper knife valve using a knife valve, closing the upper knife valve, and then injecting an inert gas such as nitrogen or carbon dioxide into the space between the two valves to remove oxygen, and In the removed state, the lower knife valve is opened to supply fuel stored in the temporary hopper space into the gasification reactor so that gasification occurs.
  • the inside of the gasification reactor is partitioned into a gasification chamber 20 on the upper side and an introduction chamber 30 on the lower side by the rotary stocker 40.
  • the gasification chamber 20 is a chamber in which gasification is performed by burning and pyrolyzing fuel supplied from a fuel inlet into an intermediate region and an upper region in a gasification reactor.
  • the gasification chamber is gasified by the combustion and pyrolysis of the fuel stacked by the gasifier supplied from the bottom.
  • the ash burner layer 22 and the combustion layer 23 which have completed combustion are formed in a portion adjacent to the rotary stocker 40, and a pyrolysis layer 24 which is pyrolyzed by receiving combustion heat is formed on the combustion layer.
  • a drying layer 25 is formed on the pyrolysis layer to dry the fuel injected by the lower heat to facilitate pyrolysis, and a space is formed on the drying layer to collect pyrolyzed syngas and water vapor generated from the drying. do.
  • the synthesis gas discharge port 21 is formed on one side of the upper side of the gasification chamber to discharge the pyrolyzed synthesis gas.
  • the introduction chamber 30 is a region located below the gasification reactor, and supplies gasifier to the upper gasification chamber, or collects ashes in which pyrolysis and combustion are completed.
  • a gasification agent introduction port 31 for introducing a gasification agent from the outside and a ash discharge port 32 for discharging the collected ash is formed on the side of the introduction chamber.
  • the transfer screw 33 is further installed in the lower portion of the introduction chamber to facilitate the discharge of the collected ash to push the collected ash with a screw to be discharged to the ash discharge outlet (32).
  • the transfer screw may be installed horizontally on the lower surface of the introduction chamber to be discharged or installed to have a predetermined angle upward, for example, an upward angle of 45 degrees to allow discharge. In this transfer, the ash is externally discharged when the ash is introduced into the screw, but when the ash component is agglomerated, the tunnel is formed so that the ash is not introduced into the screw. It is to facilitate the introduction into the furnace.
  • the rotary stocker 40 is interposed between the gasification chamber 20 and the introduction chamber 30 and partitions the two spaces.
  • the grid-shaped grate 41 having a plurality of through holes is formed by the rotation shaft 42. It is installed to be rotatable.
  • the Great 41 is formed in one or multiple stages to rotate and evenly supply the gasifier through the Great while rotating, and the ash and wood-based mass of the combustion and pyrolysis is crushed to facilitate the discharge to the bottom.
  • the rotary shaft 42 is to be expressed to the outside by inserting the lower end of the gasification reactor, thereby receiving the power from the motor to be rotated.
  • the swirling gas inlet 50 is provided with a gasifier injection pipe in communication with the gasifier to supply a swirl, and the supplied gasifier is supplied to the stacked fuel combustion layer and the pyrolysis layer to promote gasification and complete combustion. do.
  • the additional swirl gasifier is supplied only when the gasifier is supplied only through the introduction chamber 30.
  • the gasifier is not evenly supplied and combustion is only partially performed and pyrolysis is performed.
  • the heat supply to the layer is also lowered, which causes a problem of lowering the thermal decomposition efficiency. Therefore, by additionally supplying the gasifier through the swinging gas inlet 50 having a different supply direction than the primary, the gasification agent is supplied in various directions to minimize the thermal decomposition efficiency caused by the channeling phenomenon. Can be.
  • the additional gasifier is supplied while turning the inner wall of the gasification chamber 20, the passage time and the contact area of the combustion layer and the pyrolysis layer are increased to increase the gasification efficiency.
  • the swiveling gas inlet 50 may be disposed at the same plane on the same plane in addition to the four, or arranged in two rows above and below, so that the gasifier can be supplied as uniformly as possible.
  • the portion of the synthesis gas discharge port 21 of the gasification chamber 20 is further provided with a catalyst chamber 60 is further decomposed by the catalytic reaction tar component contained in the discharged syngas Can be converted to syngas.
  • the catalyst chamber 60 includes a side wall 61 partitioning the gasification chamber and a space, a lower porous plate 62 through which the gasified synthesis gas is introduced from the gasification chamber, an inner wall surface of the gasification reactor, and the side wall and the porous plate. It is made of a tar conversion catalyst 63 is filled in the space formed as.
  • the side wall 61 is deflected from the central axis of the gasification reactor 3 to the outer shell so as not to interfere with the fuel supply through the fuel inlet 10, and the lower porous plate 62 has a smaller diameter hole than the catalyst.
  • 621 is preferably formed from a plate or mesh formed.
  • the tar conversion catalyst 63 to be filled may be selected from any one or two or more of alumina, silica, dolomite, olivine.
  • the dispersion cap 64 may be further installed in the through hole 621 of the porous plate 62.
  • the porous plate 62 is formed of a vertical pipe 641 in communication with the through hole 621 is installed vertically and a conical cap 642 spaced a predetermined distance from the top of the vertical pipe.
  • the lower end of the conical cap (642) is located below the upper end of the vertical pipe to prevent the catalyst 63 is discharged through the vertical pipe 641, the syngas discharged to the top of the vertical pipe While moving downward along the inner surface of the conical cap (642) to increase the passage length so as to move upward through the bottom of the conical cap discharged to the syngas outlet 21 to increase the reaction time with the catalyst.
  • the combustion and pyrolysis is made at a temperature of 700 ⁇ 1000 °C gasified syngas has a high temperature of 400 ⁇ 500 °C.
  • the high temperature synthesis gas contains a small amount of tar components therein, the tar component is decomposed into a combustible gas by the tar conversion catalyst 63 while passing through the catalyst chamber 60 together with the vapor evaporated in the drying process.
  • the cyclone 4 passes through the syngas discharged through the syngas discharge port 21 of the gasification chamber 20 to separate and remove a small amount of ash or water, such as steam, contained in the syngas, and then remove the cyclone. Synthetic gas removed by the foreign matter to lower the temperature through the heat exchanger (5).
  • the fuel inlet 10 of the gasification reactor 3 opens and closes the fuel while opening and closing the double valve 11 sequentially. Supply to the gasification chamber 20.
  • the fuel laminated in the gasification chamber 20 of the gasification reactor is burned by the gasification agent supplied through the introduction chamber 30 and the rotary stocker 40, and the ash layer 22 and the combustion layer 23 from the bottom to the top. ),
  • the pyrolysis layer 24 and the dry layer 25 are formed sequentially. That is, the pyrolysis is performed by the burned heat, and the fuel is dried while the residual heat of the pyrolysis and the high temperature synthesis gas rise.
  • the gasifier is supplied while turning the inner wall of the gasification chamber 20 through the swinging gas inlet 50 so that the contact time between the gasifier and the combustion layer or the pyrolysis layer is increased and uniformly supplied. Improve the pyrolysis effect by ensuring even pyrolysis at.
  • the gasified syngas passes through the catalyst chamber 60 formed inside the gasification reactor and converts a small amount of tar contained in the syngas into flammable gas, and the syngas discharged is discharged from the cyclone 4 and the heat exchanger. While passing through (5) sequentially, keep foreign substances and temperature lower.
  • the rotary stocker 40 is rotated by receiving power to discharge the ash is completed combustion to the introduction chamber 30, the ash collected in the introduction chamber is discharged through the ash discharge port (32).
  • Gasification reaction experiment was performed using the fixed bed gasifier according to the present invention.
  • gasifier injection was performed both through the introduction chamber and through the secondary gas injection port.
  • the injected fuel was tested with water 8.78%, 75.07% volatile matter, 15.89% fixed carbon, 0.26% ash, and the gasification chamber was operated stably at 800 ° C.
  • the present invention relates to a fixed bed biomass gasifier with a swirl gas inlet, which is applicable to the biomass gasifier industry.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

La présente invention concerne un gazéifieur de biomasse à lit fixe doté d'un orifice d'injection de gaz tourbillonnant. Plus précisément, un agent de gazéification est introduit de manière tourbillonnante par un orifice d'injection de gaz tourbillonnant formé sur la partie inférieure d'un réacteur de gazéification dans lequel une réaction de gazéification est réalisée par l'introduction d'une biomasse lignocellulosique, la gazéification étant ainsi accélérée en raison de l'augmentation de la durée de contact entre l'agent de gazéification tourbillonnant et une couche de pyrolyse. En outre, une chambre contenant un catalyseur est située dans la partie supérieure de celui-ci, dans laquelle un orifice de sortie est formé, la chambre servant à convertir le goudron contenu dans le gaz de synthèse déchargé en gaz de synthèse supplémentaire.
PCT/KR2013/000305 2012-02-27 2013-01-15 Gazéifieur de biomasse à lit fixe doté d'un orifice d'injection de gaz tourbillonnant WO2013129771A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020120019931A KR101363270B1 (ko) 2012-02-27 2012-02-27 선회식 가스주입구가 형성된 고정층 바이오매스 가스화장치
KR10-2012-0019931 2012-02-27

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WO2013129771A1 true WO2013129771A1 (fr) 2013-09-06

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WO (1) WO2013129771A1 (fr)

Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
KR101632146B1 (ko) * 2015-03-31 2016-06-21 (주)정석이엔씨 바이오매스 가스화 장치
KR101655844B1 (ko) * 2015-09-10 2016-09-08 주식회사 대원지에스아이 무유동매체 업드래프트형 열분해 가스화 반응로
KR101938372B1 (ko) 2017-08-31 2019-01-14 고등기술연구원 연구조합 역청원료의 열분해 장치
KR102451467B1 (ko) * 2020-05-11 2022-10-12 비엔지코리아(주) 바이오매스를 저온열분해에 의해 제조하는 연료용 수성가스 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000178567A (ja) * 1998-12-16 2000-06-27 Hitachi Ltd 石炭ガス化複合発電プラントおよび石炭ガス化ガス精製設備
JP2003089794A (ja) * 2001-09-19 2003-03-28 Hitachi Ltd 有機性廃棄物用ガス化炉および有機性廃棄物ガス化発電装置
KR100784851B1 (ko) * 2007-01-12 2007-12-14 한국에너지기술연구원 저타르 배출형 바이오매스 가스화 장치
KR100896933B1 (ko) * 2008-05-30 2009-05-14 한국에너지기술연구원 목질계 바이오매스 자원을 이용하는 회전식 스토커 가스화반응기를 구비한 가스화시스템
KR20110054947A (ko) * 2009-11-19 2011-05-25 한국에너지기술연구원 왕겨 가스화장치 및 그 장치를 이용한 합성가스 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000178567A (ja) * 1998-12-16 2000-06-27 Hitachi Ltd 石炭ガス化複合発電プラントおよび石炭ガス化ガス精製設備
JP2003089794A (ja) * 2001-09-19 2003-03-28 Hitachi Ltd 有機性廃棄物用ガス化炉および有機性廃棄物ガス化発電装置
KR100784851B1 (ko) * 2007-01-12 2007-12-14 한국에너지기술연구원 저타르 배출형 바이오매스 가스화 장치
KR100896933B1 (ko) * 2008-05-30 2009-05-14 한국에너지기술연구원 목질계 바이오매스 자원을 이용하는 회전식 스토커 가스화반응기를 구비한 가스화시스템
KR20110054947A (ko) * 2009-11-19 2011-05-25 한국에너지기술연구원 왕겨 가스화장치 및 그 장치를 이용한 합성가스 제조 방법

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KR20130098092A (ko) 2013-09-04

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